Ionic, radical and pericyclic reactions

 Every organic reactions can be classified into one of three, more or less exclusive categories-
Ionic, radical and pericyclic

 Ionic reactions involve pairs of electrons moving in one direction e.g. Ionization of a teritiary
alkyl halide, aldol reaction

 Radical reactions instead involve the correlated movement of single electrons E.g. Photolytic
cleavage of chlorine, removal of hydrogen atom from toluene by a chlorine atom
Pericyclic reactions

 These are organic transformations which proceeds via either intramolecular rearrangement or
intermolecular interactions of molecular orbitals generating cyclic transition states, through
which continuous flow of electrons results in concerted creation or breaking of bonds

 These reactions are activated by heat (thermal) or light (photochemical).

 Products through thermal and photochemical transformations are generally different in their
stereochemistry.
 These reactions are insensitive to solvent polarity and free radical initiators or inhibitors.
 They always follow lowest energy path even if difference between symmetry
allowed or symmetry forbidden transition is very small; otherwise they will not occur
in concerted manner.
Molecular Orbitals and Their Symmetry Properties
 In pericyclic reactions, the reactivity of the reactions can be explained on the basis of
Perturbational Molecular Orbital (PMO) theory.

 The basic postulate of PMO theory is that a chemical reaction takes place by the perturbation
of molecular orbitals (MOs) of reactants on heating and on irradiation with light.
 The MOs that are formed by the linear combination of atomic orbitals (LCAO).

 The MOs, those are more stable than the component atomic orbitals are called bonding
molecular orbitals (BMOs), and other is antibonding molecular orbitals (ABMOs), less stable
than the component orbitals.

 Two π molecular orbitals are of particular importance in understanding pericyclic reactions.

 One is the occupied molecular orbital of highest energy, known as highest occupied
molecular orbital (HOMO). The other is the unoccupied molecular orbital of lowest energy
known as lowest unoccupied molecular orbital (LUMO). These are collectively called frontier
molecular orbitals (FMOs)

 The electrons in the HOMO of a molecule can be removed with the least expenditure of energy

 The LUMO of a molecule is the orbital to which electrons can be transformed with the least
expenditure of energy.
Molecular Orbitals of ethylene

 Two unhybridized 2p orbital from each carbon atoms combines to form two pi molecular orbitals,
one a low-energy pi bonding orbital and one a high-energy pi* antibonding orbital.

 The two paired electrons of the π-bond are placed in the bonding MO, which is the Highest
Occupied Molecular Orbital (HOMO).

 The antibonding MO is the Lowest Unoccupied Molecular Orbital (LUMO) and contains no
electrons. The HOMO and LUMO are called frontier MOs (FMOs).

 In ground state the HOMO has no node and it is symmetrical (S) with respect to a mirror
plane orthogonal to the sigma bond while the LUMO has one node and it is
antisymmetric (A) in the mirror plane.
Molecular Orbitals of 1,3-butadiene
 For 1,3-butadiene there are four MOs, two bonding and two antibonding (Fig. 4). Each
successive, higher energy MO has an additional node. The HOMO is π2 while the LUMO is π3*.

 The energy gap between the HOMO and the LUMO is 131 kcal/mol (214 nm), less than that for
ethylene. Promotion of a bonding HOMO electron to the LUMO is effected by UV light. It is
called a π --> π* transition.
Molecular Orbitals of 1,3,5-hexatriene
 There are six adjacent carbon atoms involved in the pi system and the combination of a p
orbital from each of these six atoms will result in six pi molecular orbitals: ψ1, ψ2, ψ3, ψ4*, ψ5*,
and ψ6* (also referred to as π1, π2, π3, π4*, π5*and π6*).

 Orbitals ψ1, ψ2 and ψ3 are bonding molecular orbitals and are occupied in the ground state with
ψ3 being the Highest Occupied Molecular Orbital (HOMO).

 ψ4*, ψ5*, and ψ6* are antibonding molecular orbitals and are unoccupied in the ground state
with ψ4* being the Lowest Unoccupied Molecular Orbital (LUMO).

 The HOMO-LUMO gap (π --> π* transition) in the hexatriene has dropped to 109 kcal/mol (258
nm) and the wavelength of absorption has increased.
Molecular Orbitals of allyl system
 The allyl cation, allyl anion and allyl radical all have the same orbitals, but each system contains
a different number of electrons.
 The MOs of the allyl system can be constructed by the interaction three orbitals (linear
combination of ethylene MOs with a third C 2p orbital)
 The ethylene bonding orbital, π gives linear combination with the p orbital in a bonding way
and moving down in energy to give ψ1.
 The ethylene antibonding orbital (π*) gives linear combination with p orbital in an antibonding
way and moving up in energy to give ψ3*.
Molecular Orbitals of 1, 3-pentadienyl system
 The pentadienyl cation, pentadienyl anion and pentadienyl radical all have the same orbitals,
but each system contains a different number of electrons.

 No. of orbitals interacting = 5

 Electrocyclic reactions

 An electrocyclic reaction is defined as the thermal or photochemical conversion of an acyclic

conjugated system into a ring system by formation of a σ bond between the ends of the
conjugated system in a concerted process, or the reverse of this reaction.

 Either a ring is formed with the generation of a new σ bond and the loss of a π bond (i.e., gain
of one σ bond and loss of one π bond) or ring is broken with the loss of one σ bond and gain of
one π bond.

 Thus electrocyclic reactions can be classified into two categories

i) Electrocyclic opening of the ring, and

(ii) Electrocyclic closure of the conjugated system.

 There are two possible pathways for the ring-opening and ring-closing of electrocyclic reactions
which can determine the stereochemistry of product formed. They are:

1. Conrotatory process (or motion), and

2. Disrotatory process (motion).
Electrocyclic reactions
Conrotatory and disrotatory motion in ring-closing reactions

 When an electrocyclic reaction takes place, the carbon at each end of the conjugated π system
must turn in a concerted fashion so that the p orbitals can overlap (and rehybridised) to form σ
bond that closes the ring.

HOMO

 The rotation can occur in either same directions or opposite directions depending on the
symmetry of HOMO
 Electrocyclic reactions
Conrotatory and disrotatory motion in 4π electron ring-closing reactions

 Under thermal conditions HOMO terminal lobes and groups on the two carbon atoms turn in the
same direction (clockwise or counter-clockwise) resulting in ring closure (conrotatory motion)

cis
HOMO

 Under photochemical conditions 1e- from the ψ2 BMO can be excited to ψ3, ABMO. Thus the
HOMO under consideration will be ψ3

HOMO
 Electrocyclic reactions
Conrotatory and disrotatory motion in 4π electron ring-closing reactions

 The terminal lobes of highest occupied molecular orbitals and groups of the two carbon atoms turn
in the opposite directions (clockwise or counter-clockwise) resulting in ring closure under
photochemical conditions

trans
Electrocyclic reactions
Conrotatory and disrotatory motion in (4n+2) π electron ring-closing reactions

 Under thermal conditions ψ3 is the ground state HOMO of 1, 3, 5-hexatriene which has m-
symmetry. Therefore, the thermal cyclisation proceeds by disrotatory motion.

 Under photochemical coditions one electron from ψ3 BMO is promoted to ψ4* and it
becomes the HOMO. This excited state HOMO has C2-symmetry.Therefore, photo-
induced cyclisation proceeds by conrotatory motion.
Electrocyclic reactions
Conrotatory and disrotatory motion in 1,3,5-hexatriene ring-closing reactions
 Thermal induced closure of (2E, 4Z, 6E)-2, 4, 6-octatriene involves the disrotatory motion to
form the sigma bond

 During the photoinduced closure of (2E, 4Z, 6E)-2, 4, 6-octatriene the excited state HOMO
involved is ψ4* which has C2-symmetry. Therefore, conrotatory motion is required for σ
(sigma) bond formation.
Electrocyclic reactions
Summary of the type of motion to be expected from different polyenes under thermal
and photochemical conditions

Mirror plane
Mirror plane
Symmetry (HOMO)
System Symmetry (HOMO)
Excited
ground

4n π A S

4n+2 π S A
Electrocyclic reactions
Problem-1

Which one of the following electrocyclic reactions should occur readily by a concerted mechanism?

Solution: Reaction 1 is a disrotatory reaction involving (4n + 2)π electrons because this will
give cis product. This reaction is allowed reaction. This reaction, therefore, can occur
readily by a concerted mechanism.

Reaction 2 is a conrotatory reaction involving (4n + 2)π electrons because conrotatory

motion will give trans product. It does not allow because the reaction is symmetry
forbidden reaction. Thus, the reaction does not occur readily.
Electrocyclic reactions
Problem-2

Complete the following reaction and give stereochemistry of the product.

Solution: Reaction is photo-induced reaction. Reactant has (4n + 2)π electrons. Its excited
HOMO is ψ4* which has C2-symmetry. Thus, motion is conrotatory motion.
Electrocyclic reactions
Problem-3
Complete the following reaction and give stereochemistry of the product.
Electrocyclic reactions
Problem-4

Solution

 Dienyl cations and dienyl anions both undergo electrocyclic ring closure

 When the cyclooctadiene is deprotonated with butyllithium it generates an dienyl anion. There
are five p orbitals and six π electrons in the dienyl anion which undergo ring closure in a
disrotatory manner.

 In this case, it is the conrotatory photochemical cyclization that is prevented by strain as the
product would be a 5,5 trans-fused system.
Electrocyclic reactions
Conrotatory and disrotatory motion in ring opening reactions

 The most common example of the ring opening reaction is the conversion of cyclobutene to
1, 3-butadiene.

 This conversion can only be possible if a σ (sigma) bond between C3—C4 of cyclobutene must
break during the course of the reaction.
 This σ (sigma) bond may break in two ways. First, the two atomic orbital components of the
σ (sigma) bond may both rotate in the same direction, clockwise or counter-clockwise. This
process is known as conrotatory motion

 Second, the atomic orbitals may rotate in opposite directions, one clockwise and the
other counter-clockwise. This process of ring-opening is known as disrotatory motion
Electrocyclic reactions
Conrotatory and disrotatory motion in ring opening reactions
 Under thermal condition if the ring opening generates a conjugated polyene containing 4n
π electrons the rotation should be done in such a way that it generates an asymmetric MO.
i. e. it proceeds via a conrotatory motion

 Similarly if the ring opening generates a 4n π conjugated polyene under light irradiation the
rotation should be done in such a way that it generates a symmetric MO. i. e. it proceeds
via a disrotatory motion

 Under thermal condition if the ring opening generates a conjugated polyene containing
(4n+2) π electrons the rotation should be done in such a way that it generates a symmetric
MO. i. e. it proceeds via a disrotatory motion

 Photochemically if the ring opening generates a conjugated polyene containing (4n+2) π

electrons the rotation should be done in such a way that it generates an asymmetric MO. i.
e. it proceeds via a conrotatory motion
Electrocyclic reactions
Summary of the type of motion to be expected from different polyenes under thermal and
photochemical conditions
Electrocyclic reactions
Electrocyclic ring-closure given by allyl carbanion

 Allyl carbanion is a 4nπ conjugated system.

 Conrotatory motion is the mode of cyclisation in the thermal condition.

 Disrotatory motion is the mode of cyclisation under the photochemical condition.

Electrocyclic reactions
Reactions given by allyl carbocation
 Cyclopropyl cations are virtually unobservable, as ring strain encourages them to undergo
electrocyclic ring opening to give allyl cations. Even as they start to form as intermediates,
they spring open to give allyl cation derived products.

 For example during the hydrolysis of cyclopropyl tosylates removal of the tosylate (-OTs) and ring
opening occur simultaneously,

 Since the number of participating electrons are 2 the reaction is disrotatory.

Electrocyclic reactions
Reactions given by allyl carbocation
 Cyclopropyl cations are virtually unobservable, as ring strain encourages them to undergo
electrocyclic ring opening to give allyl cations. Even as they start to form as intermediates,
they spring open to give allyl cation derived products.

 For example during the hydrolysis of cyclopropyl tosylates removal of the tosylate (-OTs) and ring
opening occur simultaneously,

 Since the number of participating electrons are 2 the reaction is disrotatory.

Example-1
Reactions given by allyl carbocation

Example-2

Example-3
Electrocyclic reactions
Nazarov cyclization reaction
 Acid-catalyzed cyclization of divinyl ketone to afford Cyclopentenones is known as Nazarov
cyclization reaction

 The reaction proceeds via generation of a 3-hydroxy pentadienyl cation which undergoes
conrotatory cyclization to furnish the product

 One of the fi ve π orbitals involved is empty—so the cyclization is a 4π electrocyclic

reaction,and the orbitals forming the new σ bond via conrotatoty cyclization.
Electrocyclic reactions
Torquoselectivity

 Torquoselectivity is a special kind of stereo selectivity observed in electrocyclic reactions as the

preference for inward or outward rotation of substituents in disrotatory or conrotatory reactions.

 In such cases, the driving force for the selectivity is steric strain.

 Studies have revealed that the selectivity changes by the presence of either electron donating
or electron withdrawing groups.
Electrocyclic reactions

Problem 1

Explain different behaviour of the following reaction under thermal and photochemical conditions.
Electrocyclic reactions

Problem 2
Treatment of following imine with base followed by an acidic work-up gives a cyclic product with
two phenyl groups cis to one another. Explain?

The proton from the middle of the molecule is removed to give an anion stabilized by two
nitrogens and three phenyl groups. A six-electron electrocyclic reaction closes the five-
membered ring and this must be disrotatory, moving both phenyl groups up (or down).
Cycloaddition reactions
 A cycloaddition is a reaction in which two unsaturated molecules undergo an addition reaction to
yield a cyclic product.
 Formation of cyclic product takes place at the expense of one π (pi) bond in each of the reacting
partner and gain of two σ (sigma) bonds at the end of the both components having π ( pi ) bonds.
 Thus, in this reaction there is loss of two π (pi) bonds of the reactants and gain of two σ (sigma)
bonds in the product.

Example 1

Example 2

 The cycloaddition reactions are classified with respect to three facts of the reaction:

(i) The number of electrons of each unit participating in cycloaddition.

(ii) The stereochemical mode of cycloaddition (supra, syn or antara, anti).
Cycloaddition reactions
 Example 1 is a [2 + 2] cycloaddition reaction because the reaction involves two electrons from one
reacting component and also two electrons from the other. Example 2 is a [4 + 2] cycloaddition.

 A cycloaddition may in principle occur either across the same face or across the opposite faces
of the planes in each reacting component i. e. via interaction HOMO of a reactant with LUMO of
other

 If both newly formed bonds are generated by attack from the same face of the π system the
formation is called suprafacial.
 However, if attack occurs from opposite sides of the π system, the orientation of the
newly formed bonds is called antarafacial.
Cycloaddition reactions
 The π systems of both components are nearly parallel during the supra-supra facial attack
([πns+πns]), thus allowing for optimal overlap of the orbitals.

 In the case of an antara-supra facial attack, the π system of the antarafacial component is initially
located vertical to the suprafacial reacting partner ([πns+πna]).

 For steric reasons, such an arrangement is difficult to realize in most cases and the overlap is
less effective. Therefore, supra-antara cycloadditions are relatively rare, even when allowed.

 An antara-antara overlapping configuration of reaction partners is even more difficult to achieve

([πna+πna]). Such a reaction is not known experimentally, it is a purely hypothetical example.
Cycloaddition reactions
[2 + 2] cycloaddition reactions
(A) Thermal Induced [2 + 2] Cycloaddition Reactions

 When ethylene is heated, its π electrons are not promoted, but remain in the ground state ψ1

 The thermal reaction of two ethene molecules (one is HOMO and other is LUMO) is orbital
symmetry forbidden process for its suprafacial–suprafacial [π2s+π2s]-cycloaddition,

 During suprafacial–antarafacial [π2s+π2a] mode of HOMO-LUMO interactions there is the

possibility of bonding overlap at both ends.
 But there is antibonding at the other two corners. Overall there is no net bonding.

 Ethylenes doesn’t undergo thermal Induced [2 + 2] Cycloaddition reactions

Cycloaddition reactions
(B) Thermal Induced [2 + 2] Cycloaddition Reactions of ketenes

 Ketenes undergo [2 + 2] cycloaddition reactions with ketenes under thermal conditions to

affiord cyclobutanone derivatives

 Ketenes carry an additional p orbital at one end of the LUMO (at the sp-carbon). It overlaps
with the both orbitals of the HOMO in alkenes making overall bonding interactions four. This
favors the reaction

 Here the HOMO-LUMO interactions take place suprafacial with respect to alkene and
antarafacial with respect to ketene
Example
Cycloaddition reactions
(B) Thermal Induced [2 + 2] Cycloaddition Reactions of ketenes
Cycloaddition reactions
(c) Photoinduced [2 + 2] Cycloaddition Reactions of Alkenes

 Alkenes undergo [ 2 + 2] cycloaddition reactions readily under light irradiation to afford

cyclobutane derivatives

 When ethylene is irradiated with photon of UV light, a π electron is promoted from ψ1 to ψ2*
orbital in some, but not all, of the molecules. The result is a mixture of ground state and
excited state ethylene molecules.

 The interaction between HOMO of one molecule and ground state LUMO of other molecule
proceeds via supra-suprafacial pathway ([π2s+π2s]).

 It is symmetry allowed and forms a well explored area in photochemistry

 Stereochemical integrity is maintained in cycloaddition reaction because reaction is concerted.

Cycloaddition reactions
Cycloaddition reactions
[4 + 2] cycloaddition reactions
 Diels-Alder reaction is the best known [4 + 2] cycloaddition reaction.

 Diels-Alder reactions occur between a conjugated diene and an alkene (or alkyne), usually
called the dienophile.

 The reaction is thermally allowed but photochemically forbidden.

 According to the frontier orbital concept the DA reaction proceeds via either HOMOdiene-
LUMOdienophile or HOMOdienophile-LUMOdiene interactions.

 Lower HOMO-LUMO energy gap gives better overlap in TS resulting in enhanced reaction rates.

 For example the electron-deficient dienophile has a low-energy LUMO and the electron-rich
diene has a high-energy HOMO so this combination gives a better overlap
Cycloaddition reactions
[4 + 2] cycloaddition reactions under thermal conditions
 In the ground state itself, HOMO and LUMO components the of the reactants are in
phase and a bonding interaction can occur in a supra-suprafacial manner, [π4s+π2s].

 In "normal" electron demand DA reaction, the more important interactions is that between
the electron-rich diene's ψ2 as the highest occupied molecular orbital (HOMO) with the
electron-deficient dienophile's π* as the lowest unoccupied molecular orbital (LUMO).

 In an inverse (reverse) electron-demand DA reaction, EWGs on the diene lower the

energy of its empty ψ3 orbital and EDGs on the dienophile raise the energy of its filled π
orbital sufficiently that the interaction between these two orbitals becomes the most
energetically significant stabilizing orbital interaction.
Diels-Alder reactions
Diene
 The diene component in the Diels–Alder reaction can be open-chain or cyclic and it can have
many different kinds of substituents.
 The diene component must have s-cis conformation.

 Butadiene normally prefers the s-trans conformation with the two double bonds as far
away from each other as possible for steric reasons.
 The barrier to rotation about the central σ bond is small (about 30 kJ mol−1 at room
temperature) and rotation to the less favourable but reactive s-cis conformation is rapid.

 Dienes permanently in the s-trans conformation cannot undergo Diels–Alder reactions

Diels-Alder reactions
Dienophile
 They have an electron-withdrawing group conjugated to the alkene.
 Otherwise there must be some extra conjugation—at least a phenyl group or a chlorine atom
 The reaction between butadiene and a simple alkene (even ethylene) occurs in only poor yield.

 Attempts to combine even such a reactive diene as cyclopentadiene with a simple alkene lead
instead to the dimerization of the diene.
Diels-Alder reactions
(a) Stereochemistry of the adduct due to stereochemistry of the dienophile

 The Diels-Alder reaction is stereospecific. Substituents that are cis in the dienophile remain cis in
the product; substituents that are trans in the dienophile remain trans in the product.
Diels-Alder reactions
(b) Stereochemistry of the adduct due to stereochemistry of the dienophile

 The product stereochemistry is controlled by the geometry of the diene.

 Terminal vinylic carbons (1 and 4 in butadiene) of the s-cis diene contain two substituents.
One is designated as outside group and other is designated as inside group of the diene.

 According to the structure of the transition state of the Diels-Alder reaction the outside
substituents of the diene are always below the plane of the new six-membered ring of the
adduct.

Example-1
Diels-Alder reactions
(b) Stereochemistry of the adduct due to stereochemistry of the dienophile

Example-2

Example-3
Diels-Alder reactions
(b) Stereochemistry of the adduct due to stereochemistry of the dienophile

Example-4

?
major

 The diastereoisomer arising from the transition state with the carbonyl groups of the dienophile
closest to the developing π bond at the back of the diene predominates.
Diels-Alder reactions
(b) Stereochemistry of the adduct due to stereochemistry of the dienophile
Endo and Exo stereochemistry
 The Diels-Alder reaction of monocyclic dienes with alkenes will produce a bicyclic ring system

 The relative stereochemistry of the alkene substituents with respect to the bridged carbon/s in the
product can be represented using terms endo or exo.

 In exo product the exo substituent points away from the more congested part, i.e., bicyclic ring

 In endo product the endo substituent points towards the more congested part. Thus steric
repulsion in endo is more than the exo. Due to this reason exo is expected to be more
stable than the endo.

 If the dienophile has a π bond bearing substituent, the endo product is formed very faster(Kinetic
product) compared to the exo product. It arises due to the secondary interactions between the π
bond in the substituent and the developing π bond at the back of the diene which lowers the
energy of the transition state. This is called the endo rule.
Diels-Alder reactions
(b) Stereochemistry of the adduct due to stereochemistry of the dienophile
Endo and Exo stereochemistry
 In the Diels–Alder reaction between cyclopentadiene and maleic anhydride only the endo
diastereoisomer is formed, and it is the less stable one.

 For cases in which the Diels–Alder reaction is reversible and therefore under thermodynamic
control, the exo product is formed
Diels-Alder reactions
(c) Stereochemistry in intramolecular DA reactions
 When diene and the dienophile are part of the same molecule then such type of molecule gives
Diels-Alder reaction known as intramolecular Diels-Alder reaction.

Case I: When electron-withdrawing group is not present on dienophile

 In this case both ring junctions are trans to each other. Thus the substituents (i.e., hydrogens) on
both fused carbons are always trans to each other.

Case II: When dienophilic part has electron-withdrawing group which is present on inner carbon of the
dienophile

 In this case both bridge hydrogens are cis to each other and perpendicular to the plane of the ring.
 Diels-Alder reactions
(c) Stereochemistry in intramolecular DA reactions

Case III: When electron-withdrawing group is present on terminal carbon of the dienophile
and geometry is trans

 In this case also mixture of two products are formed. In one product both hydrogens of the
bridge carbons are cis and in other product both are trans. EWG is always below the plane of
the ring and cis to adjacent hydrogen of the bridge carbon.

Case IV: When electron-withdrawing group is present on terminal carbon of the diene and geometry
is cis

 In this case a mixture of two products are formed. In one product both hydrogens of the fused ring
carbons are cis. In other product both hydrogens are trans. Electron-withdrawing group is always
below the plane of the ring and trans to the bridge hydrogen.
Diels-Alder reactions
Regioselectivity in Diels-Alder reactions
 Even when the diene and dienophile are both unsymmetrically substituted, the Diels-Alder
product is usually a single isomer rather than a mixture.

 The product is the isomer that results from orienting the diene and dienophile so that we can
imagine a hypothetical reaction intermediate with a “push-pull” flow of electrons from the
electron-donating group to the electron-withdrawing group.

Case I: When an electron-donating group is present at terminal carbon of the diene

 Imaginary flow of electrons in this case is as follows

 Thus, if electron-donating group is present either at C-1 or C-4 then in this case the product is
always 1, 2 and not 1, 3.
Diels-Alder reactions
Regioselectivity in Diels-Alder reactions

Case II: When electron-donating group (D) is present on the middle carbon of the diene.

 Imaginary flow of electrons in this case is as follows

 Thus, if electron-donating group is present either at C-2 or at C-3 then in this case product is
always 1, 4 and not 1, 3.
Diels-Alder reactions
Regioselectivity in Diels-Alder reactions
 Sigmatropic reaction

 Sigmatropic rearrangement involves the shift of one sigma-bonded atom or group from its
allylic type position to the distant end of the conjugated π system followed by simultaneous
shift of π electrons.

 The rearrangement is described by the order [i, j], where i specifies the number of atom or
atoms shifted and j specifies the number of atoms in the π system that are directly involved in
the bonding changes.

 If the sigma-bonded atom or group shifts from one surface of the conjugated system and arrives at
the other end of the same surface, the rearrangement is described as suprafacial

 Alternatively, if it leaves from one surface of the π system and arrives at the opposite surface, the
rearrangement is called antarafacial,
 Orbital Symmetry Analysis of [1,3]-Sigmatropic Shifts of Hydrogen
 FMO analysis of this process indicates the interaction between the frontier orbitals
of the π system and orbitals of the migrating atom or atoms.
 We will imagine that in the transition state C, the migrating H atom breaks away
from the rest of the system, which we may treat as if it were a free radical.
 In the case of 1,3-sigmatropic shift of hydrogen, π system is an allyl radical and the migrating
atom is hydrogen.
 Their frontier orbitals are allyl ψ2 (HOMO) and hydrogen 1s for thermal reaction and allyl
orbital ψ3 in photochemical reaction.

 Orbital interactions in thermal and photochemical reactions of [1,3]-sigmatropic hydrogen shift

can be represented as

 Thermal 1,3-suprafacial shift of hydrogen is forbidden from orbital symmetry considerations. The
antarafacial shift is orbital symmetry allowed process and will be a concerted process.

 symmetry-allowed antarafacial shift leads to a transition state which is extremely strained

making thermal [1,3]-sigmatropic migrations of hydrogen unknown

 Photochemically, [1,3]-suprafacial shift of hydrogen is a symmetry allowed process because the

bonding interaction takes place in the same phase of allyl group and a few such reactions are
known
[1,3]-Sigmatropic Shift of Hydrogen
Example-1

 However, most are nonconcerted (have a diradical mechanism, to which the Woodward-Hoffmann
rules do not apply).
Orbital Symmetry Analysis of [1,3]-Sigmatropic Shift of Alkyl Groups
 In the case of 1,3-sigmatropic shift of alkyl groups, π system is an allyl radical and the
migrating atom is carbon.

 Their frontier orbitals are allyl ψ2 (HOMO) and carbon 2p for thermal reaction and allyl orbital
ψ3 (HOMO) in photochemical reaction.

 [1,3]-sigmatropic carbon shift can be proceed suprafacially via interaction of the rear lobe of
the migrating carbon and terminal lobe of π system (symmetry allowed process). Thus, if the
migrating carbon was originally bonded via its positive lobe, it must now use its negative lobe
to form the new C—C bond.

 Orbital interactions in thermal [1,3]-sigmatropic carbon shift can be represented as

allyl ψ2

 If the migrating group is a chiral carbon center thermal [1,3]-sigmatropic shift results in
inversion of configuration

 Photochemically, [1,3]-alkyl shift is symmetry allowed process with retention of configuration of

alkyl carbon.

allyl ψ3
[1,3]-Sigmatropic Shift of Alkyl Groups
Example-1

Example-2

Suprafacial, inversion

Example-3

Suprafacial, retention
Orbital Symmetry Analysis of [1,5]-Sigmatropic Shift of Hydrogen
 In the case of 1,5-sigmatropic shift of hydrogen, π system is pentadienyl radical and the
migrating atom is hydrogen.

 Their frontier orbitals are pentadienyl ψ3 (HOMO) and hydrogen 1s for thermal reaction and
pentadienyl orbital ψ4 (HOMO) in photochemical reaction.

 In thermal reaction, bonding interaction is maintained in the suprafacial mode of 1,5-shift and
hence this process is symmetry allowed, while the antarafacial shift is symmetry forbidden.

 Photochemically, [1,5]-hydrogen shift in the suprafacial mode is a symmetry forbidden

process, but antarafacial shift is a symmetry allowed process

 Thus thermal rearrangements are quite common, while photochemical rearrangements are
rare.
Molecular Orbitals of 1, 3-pentadienyl system
 The pentadienyl cation, pentadienyl anion and pentadienyl radical all have the same orbitals,
but each system contains a different number of electrons.

 No. of orbitals interacting = 5

Orbital Symmetry Analysis of [1,5]-Sigmatropic Shift of Alkyl Groups
 In the case of 1,5 -sigmatropic shift of alkyl groups, π system is an pentadienyl radical and the
migrating atom is carbon.

 Their frontier orbitals are pentadienyl ψ3 (HOMO) and carbon 2p for thermal reaction and
pentadienyl orbital ψ4 (HOMO) in photochemical reaction.

 Under thermal conditions [1,5]-sigmatropic carbon shift can be proceed suprafacially (orbital
symmetry allowed process) with retention of configuration

pentadienyl ψ3

 Under photochemical conditions [1,5]-sigmatropic carbon shift can be proceed suprafacially via
interaction of the rear lobe of the migrating carbon and terminal lobe of π system (symmetry
allowed process). Thus, if the migrating carbon was originally bonded via its positive lobe, it must
now use its negative lobe to form the new C—C bond.

pentadienyl ψ4

 If the migrating group is a chiral carbon center photochemical [1,5]-sigmatropic shift

results in inversion of configuration
[1,5]-Sigmatropic Shift
Example-1

[1,5]- H
migration

Example-2

[1,5]- H
migration

Example-3

[1,5]- C
migration
Orbital Symmetry Analysis of [1,7]-Sigmatropic Shift of hydrogen
 Photochemical [1,7]-suprafacial hydrogen shifts have been also observed

HOMO, excited state

Orbital Symmetry Analysis of [1,7]-Sigmatropic Shift of Hydrogen
 In the case of 1,7 -sigmatropic shift of hydrogen, π system is an 2,4,6-heptatrienyl radical and
the migrating atom is hydrogen
 Their frontier orbitals are heptatrienyl ψ4 (HOMO) and hydrogen 1S for thermal reaction and
ψ*5(HOMO) in photochemical reaction.
 [1,7]-hydrogen shift occurs thermally in antarafacial manner( symmetry allowed) in a
flexible π system. This type of hydrogen shift is common when one part of the π system is
in the ring and other part in open chain.

HOMO, ground state

Orbital Symmetry Analysis of [1,7]-Sigmatropic Shift of carbon
 In the case of 1,7 -sigmatropic shift of alkyl groups, π system is an 2,4,6-heptatrienyl radical
and the migrating atom is carbon
 Their frontier orbitals are heptatrienyl ψ4 (HOMO) and carbon 2p for thermal reaction and
heptatrienyl orbital ψ*5(HOMO) in photochemical reaction.

 [1,7]-Suprafacial alkyl shift (symmetry allowed) is observed under thermal conditions, with
inversion at the migrating carbon center

HOMO, ground state

Orbital Symmetry Analysis of [1,7]-Sigmatropic Shift of carbon

 [1,7]-Suprafacial alkyl shift is observed under photochemical conditions, with retention in

configuration at the migrating carbon center

HOMO, Excited state

Cope rearrangement

 The thermal [3,3]-sigmatropic rearrangement of 1,5-dienes to the isomeric 1,5-dienes is called

the Cope rearrangement, and it can only be detected when the 1,5-diene substrate is
substituted.

 The rearrangement is reversible because there are no changes in the number or types of
bonds, and the position of the equilibrium is determined by the relative stability of the starting
material and the product.

 The reaction is both stereospecific and stereoselective as a result of a cyclic chair-like transition
state.

 The typical temperature required to induce Cope rearrangement in acyclic dienes is 150-260 °C.
Cope rearrangement
Mechanism and stereochemistry

 The Cope rearrangement predominantly proceeds via a chair-like transition state

 The exact nature of the transition state depends on the substituents and varies between two
extreme forms: from two independent allyl radicals to a cyclohexane-1,4-diradical depending on
whether the bond making or bond breaking is more advanced.
Cope rearrangement
Mechanism and stereochemistry
 It is sometimes used to think that after an initial homolytic cleavage that yields two allylic radicals,
the ψ2 (HOMO) of each interacts together in a suprafacial manner (symmetry allowed)
Cope rearrangement
Mechanism

 The Cope rearrangement of strained 1,2-divinyl cycloalkanes (cyclopropane and cyclobutane)

gives convenient access to synthetically useful seven- and eight-membered carbocycles.